This subproject is one of many research subprojects utilizing the resources provided by a Center grant funded by NIH/NCRR. The subproject and investigator (PI) may have received primary funding from another NIH source, and thus could be represented in other CRISP entries. The institution listed is for the Center, which is not necessarily the institution for the investigator. The Zhang group is interested in synthetic organic, inorganic and organometallic chemistry, transition metal catalyzed asymmetric reactions for the synthesis of biologically active compounds, biomimetic chemistry, molecular recognition and material chemistry. During the last few years, they accelerated effort in developing innovative chiral ligands and new reactions. While they already invented three chiral ligands (PennPhos, BICP and Ambox), the Zhang group developed fourteen new ligands (e. g., Binaphane, ketalPhos, P, N ligands, TunaPhos, DIOP*, FAP and TangPhos). These effective ligands further broaden the scope of many asymmetric reactions and will have many practical applications. Developing new transition metal-catalyzed reactions are important missions in organic synthesis. The Zhang group is evaluating Rh-catalyzed enyne isomerization to offer 1,4-dienes exclusively under a mild condition and the first highly enantioselective ene reaction was achieved. In the area of metal-catalyzed cyclization, the Zhang group has invented the first highly enantioselective Ag-catalyzed [3+2] cycloaddition for the synthesis of five-membered ring N-containing hetereocyclics. These hetereocyclics can be easily prepared from ready available aldehydes, aminoesters and dipolarphiles.